Non-terminal epoxy resins



ed Sta es a 1' 2,975,149 NON-TERMINAL EPOXY RESINS William s. Port, Norristown, Leonard L. Gelb, Philadelphia, and Waldo C. Auit, Glenside, Pa., assignors to the United States of America as represented by 'the Secretary of Agriculture N0 Drawing. Filed Mar. 2, 1959, Ser. No. 796,710

16 Claims. (Cl. 260-23) (Granted under Title 35, US. 'Code (1952), sec. 266) A non-exclusive, irrevocable, royalty-free license in the invention herein described, throughout the world for all purposes of the United States Government, with the power to grant sublicenses for such purposes, is hereby granted to the Government of the United States of America.

This invention relates to epoxy resins. More particularly, this invention relates to epoxy resins prepared by polymerization of cyclic anhydrides and compounds containing non-terminal epoxide groups.

Commercially available intermediates for thermosetting resins, useful in molding compositions for encapsulatingdelicate parts, making shaped objects, and the like, are predominantly glycidyl derivatives or contain terminal epoxide groups. Processes have been developed in which epoxy ether resins and compositions containing these resins are mixed with curing (hardening) agents and, usually with slight heating, allowed to stand until a hard, cured resin is produced. In contrast to'thefo'regoing type of epoxy resin,- compounds containing non-"- terminal epoxides, many of which have been known for 1 many years, are little used becausethese compounds are A less reactive and because the cured resins derived therefrom have low heat distortion temperatures, low tensile strengths, and low moduli of elasticity. As will be illustrated subsequently, the non-terminal epoxides and cyclic I anhydrides of the compositions of the present invention upon heating for many hours, form only viscous liquids, gels, and soft, friable solids.

We have now discovered that the addition of small amounts, that is, about from 0.1 to 4%, by weight, of a tertiary amine, such as benzyl dimethyl amine, B-dimethylaminopropionitrile, and triamylamine, to mixtures of non-terminal epoxy compounds and cyclic anhydrides gave desirable products. These products range from soluand cyclic anhydrides were reacted to hard, clear, nonsolub-le resins obtained when multifunctional epoxides or Patented. Mar. 14, 1961.

ple, ,B-propiolactone, and about from 0.1 to 4%, by.

weight, of a tertiary amine. f

An object of the present invention is to prepare epoxy resins from estersand amides containing non-terminal epoxide groups.

Another'object of this invention is to prepare improved resin products from epoxy derivatives of fats and oils.

Other objects and a fuller understanding of the invention may be had by further referral to description and claims.

Epoxidized vegetable oils may be prepared by wellknown procedures from vegetable oils containing unsaturated fatty acids. Among important vegetable oils are soybean, cottonseed, linseed, perilla, and safilower oils.

Unsaturated fatty acids such as oleic, linoleic, and linolenic may be converted. to esters using mono-, di-, and polyhydric alcohols and the resulting synthetic esters epoxidized to give a wide range of compounds containing non-terminal epoxide .groups. Non-terminally unsaturated alcohols used in the preparation of esters increases the number of sites of epoxidation.

One of the advantages of employing non-terminal epoxy gen, ha logens, silicon, and boron derivatives and carboe cyclic and heterocyclic derivatives.

The general reaction of the present invention, that of a non-terminal epoxide and cyclic anhydride in the presence of a tertiary amine, is not restricted to'cyclic carboxylic acid anhydrides such as phthalic anhydride, but is opera- I -tive with other cyclic compounds capable of producing fa propagating ion under suitable catalysis. We have used B-propiolactone in the preparation of the resin products. Other cyclic compounds which may be used are lactams, imides, sulfo-carboxylic acid anhydrides, N-carboxy an- ,h'ydrides (fromamino acids),"cyclic diureides, hydanble polymers, obtained when mono-functional epoxides' resin, but produces a different kind, of resin. For example, in place of a soft, friable, weak gel which was obtained in the absence of the tertiary amine, a hard, clear, glass-like resin was obtained when the same reactants were heated in the presence of the amine.

The linear polymers obtained by this process are useful as lubricant additives, thickening agents, or components of surface coatings. The insoluble resins are useful in making ca'st objects, molding compositions, and the like.

According to the present invention a new epoxy resin is prepared by a process comprising heating until cured, that is, until the polymerization reaction is substantially complete, a mixture of components which must be completely miscible at the temperature at which reaction is effected, said mixture of components containing an amount ranging from an equimolar equivalent to 20% greater or toins and the like. 7

In contrast to the formation of a hard resin from commercial (glycidyl) epoxy intermediates and phthalic an-. I

hydride in the absence of a tertiary amine, only weak 'friable gels or viscous liquids were obtained from nont'erminal epoxides and phthalic anhydride in the absence of tertiary amine even after longheating (Examples 14 and '16-). Optimal molar ratio of reactants, amount of initiator, reaction temperature and cure time were ob- 20% less than an equimolar equivalent of a material hava cyclic anhydride such as a cyclic carboxylic anhydride,

tained-by correlation with'heat distortion temperature, A

modulus of elasticity and tensile strength. The data in Table I illustrates.v a preliminary study to decide molar ratio of reactants. v

TABLE I Eflect of variation of phthalic qnhydride on the heat, distortion temperamredn'd modulus of elasticity of resins made from epoxidized soybean oil Heat Distortion Temp.,

lltodulusot Elasticity,

Phthaltc Anhydrlde, Mole Percent v Lbs/S 2.5% Benz mimeutyumiheciiredttnd olonbnoias.

upon 9 IrlchXl '5 aze-ea 3 A 20% excess of phthalic anhydride or a 10% excess of expoxidized soybean oil did not cause appreciable change in heat distortion temperature of the resin products. The effect upon modulus of elasticity was pro- 4 means for mechanical agitation, a thermometer, and a dropping funnel were placed 220 ml. of chloroform and 110 g. (0.0602 mole) of dipentaerythritol hexalinoleatc (iodine number 161.4). A solution of 200 g. (35.5%)

portionately greater. It appears that considerable lee- 5 peracetic acid (0.935 mole), 100 ml. glacial acetic acid way in formulation may be exercised and still obtain d diu t t was drgpped int th flask resins satisfactory for many purposes. As a result of within 1 hr. while the temperature was maintained at these Correlations, the yp conditions p oyed in 2025 C. After the peracetic acid solution had been making resins in the following x mples will be equivadded, the reaction mixture was agitated at 20 25" C. alent weights of non-terminal expoxide and cyclic anhy- 10 until there was essentially no change in the peracetic dride, that is, one mole anhydride to one epoxide equivacid concentration of the reaction mixture (about 4 alent, at 1 0 C. in the presence of 2.5% by weight hours). The reaction mixture was then poured into tertiary amine, followed by curing for 10 hours at 150 600 ml. of water. The chloroform layer was separated Individual examples y y m the general conand freed from acids by successive washings with water, ditions, particularly in the time-temperature relation dilute sodium bicarbonate solution and water. The chloships. When lower temperatures are used the rea ti n roform solution was dried over anhydrous calcium sultime must be increased to achieve a resin with about fate, filtered and the chloroform was distilled off at a the same physical characteristics. The proper curing low pressure. temperature and time for the particular mixture to be Net weight of dodecaepoxide 99.8 g. (82% yield), of reacted is readily determined by preliminary experimen- 89.7% purity based on 8.53% oxirane oxygen found tation. (calculated 9.51%); true functionality of the epoxide,

Although 2.5 (based on the weight of all reactants) 10.76 (calc.). of the tertiary amine was used to insure optimum re- Certain syntheic oleate and linoleate esters and natuaction, the presence of only 0.1% tertiary amine illusral glycerides were epoxidized in the same manner extrated its significance in the formation of resins and the cept that the equivalent amount of the requisite olefin preferred range from about 0.2 to 4% tertiary amine was substituted for dipentaerythritol hexalinoleate. The gave resins with heat distortion temperatures which were resulting yields, oxirane oxygen values, purities and true comparable with those from 2.5 tertiary amine. functionalities for these epoxides are listed in Table 11 Most of the non-terminal epoxides were prepared from under the name of the corresponding unsaturated intercarefully selected precursors. For instance, oleic acid mediate.

TABLE H Date Pertaining to Epoxlde Product Example N0. Unsaturated ester to be epoxldlzed Percent Oxlrane Epoxlde M.P., Yield, Purity, True Equiva- O. Percent; Percent Funct. lent Found Cale.

Oleates Glycol dloleate 62-53 26. 6 4. 64 5. 15 90. 0 1. 80 344 Glycerol frinl arn 01. 4 4. s4 5. 15 04. 0 2. 32 330 Pentaerythritol tetraoleste 94. 0 4. 98 5. 10 07. 7 3. 91 321 Dipentaerythritol hexaoleatc. 91. 6 4. 72 4. 96 95. 2 5. 71 330 Linoleates Methyl linoleate 31. 5-32 45. 6 a. 30 0. s2 04. s 1. 00 172 Glycol dilinoleate 74-75 54. 3 a. 0 0. 85 n1. 5 a. 66 17s Glycerol trilimleate 35-37 85.0 9. 07 9.87 02. 0 s. 52 11s Pentaerythrltol tetralinoleate 81. 2 8. 66 9. 70 80. 4 7. 15 185 Dipentaerythritol hexalinoleate. 32. 0 8. 53 9. 51 80. 7 10. 76 188 Natural GZg/ceridea 10 Neatsfoot oll 97.3 4.06 4.35 03.2 304 11..- Lard oil I 96.0 4.15 4.46 03.0 ass 12 Soybean 011 d 5. 91 270 13 Perilla il 84.0 9.04 10.45 86.5 177 I Method of Durbetaki, Anal. Chem. 28, 2000 (1956).

b 1600/% oxirane oxygen found. I Based on iodine value of the unsaturate. d Epoxidized product from commercial sources.

of low saturates content was prepared by distilling com- EXAMPLE 4 Dipentaerythritol hexalinoleate was expoxidized by a modification of the method of Findley, Swern and Scan? Ian [1. Am. Chem. Soc. 67, 412 (1945)]. Into a one Several examples are presented to illustrate the importance of the tertiary amine in initiating the reaction to produce the new epoxy resins.

EXAMIPLE 14 A solution of epoxidized soybean oil (oxirane oxygen 5.91) 13.6 g. (0.05 equivalent) and 7.4 g. (0.05 mole) phthalic anhydride was heated at 160 C. Gelation occurred after about 1.5 hours and a rubbery product which was soft and friable resulted in two hours. After being heated for a total of six hours it was still soft and friable and when cooled was a white cloudy easily-broken mixture. Curing times 'up to 22 hours did not improve the physical properties of the product. The presence of many discrete crystals of phthalic anhydride at this time showed that very little or no reaction had occurred be:

liter, three neck, round bottom flask equipped .With a tween the epoxy compound and the anhydride. A simi-,

lar mixture of epoxidized soybean oil and phthla lic an was cured at 150 C. for 8 hours, yielding a very hard,

rigid, transparent resin.

A similar mixture, but with the benzyldimethylamine' omitted, gelled in 17 minutes and, under the same conditions of cure, gave a flexible, black opaque substance.

EXAMPLE 16 2.78 g. of hexachloroendotetrahydrophthalic anhydride and 1.11 g. phtha'lic anhydride (total of .015 mole anhydride) were melted at 150 C. in a small test tube; To the melt was added 5.79 g. (0.015 equivalent) epoxidized lard oil and 0.25 ml. of benzyldimethylamine. The mixture was stirred and heated at 1502C. for 2 hrs. after gelation (14 minutes), then at 120 C. for 24 hrs. The resulting resin was hard, transparent and flexible.

A similar mixture without the tertiary amine gelled in 1.5 hrs. and resulted in a soft, friable opaque material with discrete crystals of anhydride visible. 7

From the foregoing it is readily apparent that the presence of the tertiary amine makes possible a product which cannot be obtained by the alternative of prolonged curing in the absence of the tertiary amine.

The following examples illustrate typical preparations of epgxy resins from the non-terminal epoxides listed in Table II. Methyl oleate was found satisfactory as a mold release agent.

EXAMPLE 17 To a 9 mm. x Pyrex tube, closed at one end, coated with a film of methyl oleate, was added 3.1 g. (.021 mole) of phthalic anhydride. The tube was heated at 150 C. until the anhydride was melted. 3.9 g. (0.021 equivalent) of the octa-epoxicle of pentaerythritol tetralinoleate (Example 8) of Table II was weighed in.

a small test tube and heated at 150 C. for 5 minutes. The hot epoxide was poured into the molten anhydride and mixing was accomplished by inverting'the tube. To this mixture was added 0.2 ml. of benzyldimethylamine. The tube was heated at 150 C. for 8 hrs. after gelation which took 4 minutes. The resulting resin was transparent, amber colored, glassrlike and hard. Its physical properties were determined and are reported in Table III.

EXAMPLE 18 A 9 mm. x 10" Pyrex tube, closed at one end, coated with a film of methyl oleate, was .filledwith 2.66 g. (.018 mole) of phthalic anhydride and 5.76 g. (.018 equivalent) of the tetraepoxide of pentaerythritoltetra oleate (Example 3, Table II). The tube was immersed in a 150 C. oil bath until the contents were molten, and then the tube was inverted several times for mixing.

To this was added 0.23 ml. of benzyldimethylamine, and

strength,'modul us of elasticity and percent elongation;

were measured and are reported in Table III.

TABLE III Prepared r em 7 Heat Tensile Modu- Percent Example No. Epoxide Distortion Strength, lus of Elpgga ofEx- Tempera- 1bs./sq.in. Elasticity tron I ample ture,'C. 0.-' l

1 -29 30 4.76 9.9 2 v -9. 5 9. 55 ,20, 0 3 13 1, 550 51.2 22. 5 4 42 3, 450 129 4.10 5 e4 3, 660 132 7.1 6 79 6, 200 172 4.3 7 as 6,500 152 5.3 8. 90.5 4,160 312 a 1.5 9 1-23 3, 530 265 2. 2 10 -s. 0 70 8.13 11.1 11 9. 5 100 8. 65 17.2 12 49 2,685 2.0 1?; 73

Other resins were prepared by substituting the equivalent weight of the requisite .epoxides shown in Table III (Examples 19-26). Also given are the physical properties of the resulting resins.

The data of Table III shows that a wide range of physical properties are obtainable in the epoxy resi s prepared from epoxy derivatives of natural glycerides and of synthetic esters containing unsaturated fatty acids, using the process of the present invention.

It has now been found that limiting values of certain physical properties which vary with functionality, as demonstrated in the oleate series, Examples 15, 18, 19 and 20, and the linoleate series, Examples 17, 21-24, can be markedly increased by adding an additional tie-point 1 at each cross-link, although the longest distance between cross-links remains 22 to '25 carbon atoms. This is shown by comparing the corresponding members of each series, for instance, the product of Example 19 in which one of the reactants was epoxidized glycol oleate vs. the' product of Example 22 in which the corresponding reactant was epoxidized glycol linoleate.

The process of the present invention is illustrated with another type of non=terminal epoxide.

EX AM PLE 27 A solution of 5.0 g (0.051 mole) cyclohexene pxide.

(commercial),7.4 g. (0.050 mole) phthalic anhydride and 0.6 ml. benzyldimethylamine were heated at 140 -C. for A very rapid polymerization took place. The

amides for these resin reactions it was necessary to first prepare the amides and then to epoxidize them.

EXAMPLE 28 Preparation of N,N'-di0le0ylethylenediamine.Methyl oleate (651 grams, 2.20 moles) was heated to C. and was treated with 60 grams (1.00 mole) anhydrous ethylenediamine added slowly through a period of 1.5 hours. The reaction solution was kept at 100 C. for 3 M hanol hours after the completion of the addition. distilled out during the course of the reaction, a total of 97% of the theoretical amount beingcollected. When the reaction solution was cooled crude N-Nsdioleoylethylenediamine crystallized out. The crude product was recrystallized from ethanol to give a 52% yield of pure;

material M.P. 117118 C., having an iodine number 85.9, 77.2% carbon, 12.5% hydrogen, 4.62% nitrogen (calculated'values 86.5, 77.5%, 12.2% and 4.76% ,r e-

q ye w- EXAMPLE 29 Preparation of N-N'-di-(cis-9,1 O-epoxystearoyl) ethylenediamine.-Peracetic acid (0.048 mole as a commercial product which had been treated with sodium acetate to neutralize sulfuric acid present) was added (with mechanical agitation) to 11.8 g. (0.02 mole) of N,N-dioleoylethylenediamine dissolved in 75 ml. chloroform. The temperature of the reaction mixture was maintained at 2530 C. by controlling the rate of addition of the peracetic acid and by external cooling. Agitation was continued for three hours after the completion of the addition of the peracetic acid and then the reaction mixture was poured into crushed ice. The crude product which crystallized out was filtered off, washed with water until it was acid-free and was dried. When this product was recrystallized from carbon tetrachloride, N,N- di(cis-9,10-epoxystearoyl)ethylenediamine M.P. 127- 129 C., having an oxirane oxygen of 4.98 (calculated 5.16) was obtained in 48.5% yield.

EXAMPLE 31 Preparation of N,N'-dioleoyIpiperazine.-A mixture of 200 grams (0.67 mole) of methyl oleate and 29 grams (0.33 mole) of anhydrous piperazine was heated until refluxing began and the methanol which formed was distilled off. The crude product was cooled to -20 C. and was filtered. The residue was recrystallized from ethanol to give a 30% yield of N,N'-dioleoylpiperazine M.P. 37.5-38.0" C. having an iodine number 8l.8, 77.9% carbon, 12.2% hydrogen and 4.18% nitrogen (calculated values-82.7, 78.3, 12.0, 4.56 respectively).

EXAMPLE 32 Preparation of N,N-di-(cis-9,10epoxystearoyl)piperazine.-N,N'-dioleoylpiperazine was epoxidized by the method given in Example 28 to give a 93% yield of N,N'-di(cis-9,10-epoxystearoyl)piperazine M.P. 75-6 C., oxirane oxygen content 5.02% (calculated value 4.95).

EXAMPLE 33 Curing of N,N-di-(cis-9,10 epoxystearoyl)piperazine with phthalic anhydride.-A solution of 1.92 g. (0.013 mole) of phthalic anhydride and 0.15 g. benzyldimethylamine was heated at 150 C. and was thoroughly mixed with 4.12 g. (0.013 equivalent) of molten N,N'-di-(cis 9,10-epoxystearoyl)piperazine. The resulting solution gelled after 35 minutes of heating at 150 C. Cure was accomplished by heating at 150 C. for 2 hours and at 120 C. for 25 hours. The resulting resin was hard and slightly flexible.

Epoxy resins were also prepared using fl-propiolactone (anhydride of 3-hydroxypropionic acid) as the cyclic anhydride and several types of compounds as the source of the epoxide groups. Preparation of these resins is illustrated in the following examples.

EXAMPLE 34 Polymer from [i-propiolactone and styrene oxide.A solution of 3.6 g. (0.05 mole) B-propiolactone, 6.0 g. (0.05 mole) styrene oxide and 0.2 cc. benzyldimethylamine was heated at 150 C. At the end of one hour, it became slightly viscous and at the end of four hours too viscous to flow readily. At the end of 7 hours of heating, the resulting polymer had an oxirane oxygen value of 0.48% which corresponds to a 96.5% conversion. The polymer was useful for surface coatings.

EXAMPLE 35 Polymer from B-propiolactone and methyl epoxystearate.-A solution of 1.8 g. (0.025 mole) propiolactone, 0.1 cc. benzyldimethylamine and 7.82 g. (0.025 mole) methyl epoxystearate was heated for 24 hours at C. The oxirane oxygen content of the ensuing polymer was 0.66% which corresponds to an 84.3% conversion.

EXAMPLE 3e Polymer from a commercial bisphendl-glycidyl ether resin intermediate and fl-propiolactone-A solution of 5.4 g. (0.075 mole) of fi-propiolactone and 10.6 g. of a commercially available glycidyl ether of bisphenol A having an epoxide equivalent of 142 was heated to 150 C. Within two hours, the solution had, gelled and the resin was cured at 150 C. for 24 hours. A hard clear resin was formed which is useful for casting purposes. The use of a tertiary amine was not necessary in the preparation of this resin.

The following examples illustrate the procedure for preparing resins with tertiary amines other than benzyldimethylamine.

EXAMPLE 37 Preparation of a resin from epoxidized soybean oil, phthalic anhydride and p-dimethylaminopr0pionitrile.- A mixture of 5.4 g. (0.02 equivalent) of epoxidized soybean oil (5.9% oxirane) and 2.96 g. (0.02 mole) of phthalic anhydride was melted at 150 C. Three tenths cc. of p-dimethylaminopropionitrile (about 2.5% of the total weight of ingredients), was added and the components were thoroughly mixed. Gelation took place at 150 C. in 8 minutes. After the mixture had been cured for 8 hours at 150 C., a clear, hard resin was obtained.

EXAMPLE 38 Preparation of a'resin from epoxidized soybean oil, phtlzalic anhydride and triamylamine.The same mixture of epoxidized soybean oil and phthalic anhydride as that of Example 37 was treated with 0.3 cc. of triamylamine (about 2.5 of the total weight of ingredients) at 150 C. Gelation occurred in 8 minutes, and after the mixture had been cured for 8 hours at 150 C., a clear, hard resin was obtained.

We claim:

1. A process for the preparation of an epoxy resin comprising heating a mixture containing a compound having at least one non-terminal epoxide group, a cyclic anhydride selected from the group consisting of a cyclic carboxylic anhydride and a lactone, and a tertiary amine selected from the group consisting of benzyldimethylamine, p-dimethylaminopropionitrile, and triamylamine, to effect polymerization, each of said compound and said cyclic anhydride being present in said mixture in an amount ranging from an equimolar equivalent to :20% of an equimolar equivalent, said tertiary amine being present in said mixture in about from 0.1 to 4% by weight.

2. The process of claim 1 wherein the cyclic anhydride is phthalic anhydride.

3. The process of claim 1 wherein the cyclic anhydride is fl-propiolactone.

4. The process of claim 1 wherein the tertiary amine is benzyldimethylamine.

5. The process of claim 1 wherein the compound having at least one non-terminal epoxide group is an ester containing an epoxy derivative of an unsaturated fatty acid.

6. The process of claim 5 wherein the ester containing an epoxy derivative of an unsaturated fatty acid is an epoxidized vegetable oil.

7. The process of claim 5 wherein the ester containing an epoxy derivative of an unsaturated fatty acid is an epoxidized animal oil.

8. The process of claim 5 wherein the ester containing an epoxy derivative of an unsaturated fatty acid is an epoxidized oleate .ester.

9. The process of claim 5 wherein the ester containing an epoxy derivative of an unsaturated fatty acid is an epoxidized linoleate ester.

10. The process of claim 1 wherein the compound having at least one non-terminal epoxide group is an amide containing an epoxy derivative of an unsaturated fatty acid.

11. The process of claim 10 wherein the amide is an epoxidized oleamide.

12. The process of claim 1 wherein the compound having at least one nomterminal epoxide group is cyclohexene oxide.

13. A compound selected from the group consisting of N,N di-(cis-9,10-epoxystearoyl)ethylenediamine, N,N- dioleoylpiperazine, and N,N'-di-(cis-9,10-epoxystearoyl) piperazine.

'14. N,N-di (cis-9,10-epoxystearoy1)ethylenediainine.

15. N,N-dioleoylpiperazine. 16. N,N'-di-(cis-9,10-epoxystearoyl)piperazine.

References Cited in the file of this patent 

1. A PROCESS FOR THE PREPARATION OF AN EPOXY RESIN COMPRISING HEATING A MIXTURE CONTAINING A COMPOUND HAVING AT LEAST ONE NON-TERMINAL EPOXIDE GROUP, A CYCLIC ANHYDRIDE SELECTED FROM THE GROUP CONSISTING OF A CYCLIC CARBOXYLIC ANHYDRIDE AND A LACTONE, AND A TERTIARY AMINE SELECTED FROM THE GROUP CONSISTING OF BENZYLDIMETHYLAMINE, B-DIMETHYLAMINOPROPIONITRILE, AND TRIAMYLAMINE, TO EFFECT POLYMERIZATION, EACH OF SAID COMPOUND AND SAID CYCLIC ANHYDRIDE BEING PRESENT IN SAID MIXTURE IN AN AMOUNT RANGING FROM AN EQUIMOLAR EQUIVALENT TO $20% OF AN EQUIMOLAR EQUIVALENT, SAID TERTIARY AMINE BEING PRESENT IN SAID MIXTURE IN ABOUT FROM 0.1 TO 4% BY WEIGHT. 